Lubricants containing certain organolead nitrogen compounds



United States Patent 3,527,704 LUBRICANTS CONTAINING CERTAIN ORGANO-LEAD NITROGEN COMPOUNDS Warren L. Perilstein, Orchard Lake, and HaroldA. Beatty, Detroit, Mich., assignors to International Lead A furtherobject is to provide auxiliary compounds in the nature of antioxidantswhich will be compatible with the lead compounds and will substantiallyincrease the lubricating effectiveness thereof.

In general, the compounds which meet the objects set Zinc ResearchOrganization, Inc-, New Yo NY-, a forth above are represented by namesor formulas as fol- Nmembershipccorporation of New fYorkll s N l 0Drawing. ontinnation-in part o app cation er. 0. (a) Trialkyl lumbyl canamide and trialkyl lumb 1 3 52 2 1967 apphcahon 1969 cyanoguanidine inwhich t he alkyl group has 1 to l2 ca er. 0. Int. or. 010m 1/36,1/54 1omm, US. 01. 252-4911 32 Claims RCN H ll ABSTRACT OF THE DISCLOSURE \N/Organolead nitrogen compounds in which the lead is tetravalent and isattached to carbon and to nitrogen, and Pb-R in particular to lubricantscontaining such compounds efwherein fective as antiwear additives forlubricants. In many in- X=N CH stances such utlllty 1s enhanced byncorporating certain Y:CH, CQ) CR, or N when X is CH antroxldants. Amethod of preparation 1s also descrlbed RzalkYl of 1 to 12 carbon atomswherein trialkyllead hydroxide is reacted with the desired R,=phenyl andalkyl of 1 to 20 carbon atoms heterocyclic compound in an organicsolvent with the RIQ=H NH2 alkyl having 1 to 4 carbon atoms formation ofwater and the desired organolead nitrogen or plienyl compound- 5R"'=phenyl or alkyl having 1 to 20 carbon atoms 0=phenyl Thisapplication is a continuation-in-part of application (c) Ser. No.665,969, filed Sept. 7, 1967, now abandoned H which is a continuation ofapplication Ser. No. 601,321, C filed Dec. 13, 1966, now abandoned. NThe present invention relates to organolead nitrogen g compounds inwhich the lead atom is tetravalent and is H X joined directly to carbonand to nitrogen, and to lubricants C containing the same. 11 ILbR Anobject of the invention is to obtain such organolead compounds which areuseful as additives for lubricatwherein X and R have the meaning definedabove under ing oils and greases. (b), but the total number of carbonatoms included in Still another object is to devise additives which willthe groupRand'R' is at least 8. greatly enhance the lubricatingproperties of oils and Examples of the new organolead compounds aregiven greases, and the anti-Wear properties of oils and greases. 40 inTable I.

TABLE I Name Formula Number:

1 (Trimethylplumbyheyanamide (CHa)aPbNHCN 2 N-(tributylplumbyl)imidazoleH("3ll lI HC\ CH I Y 4 9)3 3 N-(tributylplumbyDbe d 1 H nz1m1 B720 8 HOc-- g II II H /0\ /CH Pb-(C4Hn)a 43-aminoN-(trlbutylplumbyl)-1,2,4-triazole NH2F1|\T 5N-(trlbutylplumbyl)benzotrlazole 161 116 \G1|\I H 5 1 L c N TABLEI-Continued 6 Name Formula 203-(n-butylamino)-N-(tributylplumbyl)-1,2,4-triazole H (C4H9)NC-N 21N-(triethylplmnbyl)cyanoguanidine 22N-(tri-n-bntylplumbyl)cyanoguanidino PREPARATION OF COMPOUNDS 17-20These compounds may be prepared by mixing tributyllead hydroxide with adesired 1,2,4-triazole in an organic solvent, followed byrecrystallization from ethanol. A more detailed description of thepreparation is found below in the discussion of the preparation ofcompounds 2-14.

In addition to the foregoing, there may be mentioned (tributylplumbyl)cyanamide, (tridodecylplumbyl) cyanamide,(trimethylplumbyl)cyanoguanidine, (tridodecylplnmbyl)cyanoguanidine, N(tributylplumbyl)-2-eicosyl imidazole and N-(tributylplumbyl)-4-butylimidazole. In the above formulas, the alkyl groups are normal unlessotherwise indicated. However, any branched chain alkyl of the samenumber of carbon atoms may be substituted. Furthermore, in order toprovide solubility of the compounds in lubricating oils and greases, itis desirable that the total number of carbon atoms in the alkyl andphenyl groups attached to the imidazole or triazole ring should not begreater than 35, and preferably not greater than 20.

Following are descriptions of the methods for preparing the compoundsidentified above.

PREPARATION OF COMPOUND 1 Trimethyllead cyanamide was prepared by addingan equimolar amount of cyanamide to trimethyllead hydroxide in ethanol.Upon concentrating the solution, the compound crystallized.

PREPARATION OF THE CYCLIC COMPOUNDS, SUCH AS COMPOUNDS 2-14, INCLUSIVE Atriorganolead hydroxide is mixed with the desired heterocyclic compound(which are available in the market) in an organic solvent, followed byrecrystallization from ethanol.

Thus in preparing N-(tributylplumbyl)imidazole (compound No. 2) anethereal tributyllead bromide solution (prepared from 1 mole of leaddichloride) was stirred withexcess of silver oxide (from 100 g. ofsilver nitrate) until bromide-free (ca. 30 min.). The precipitate ofsilver bromide was separated by filtration and to the remaining solutionthere was added 34.4 g. of imidazole (0.507 mole) with stirring todissolve the imidazole and the whole was evaporated to dryness. Theresidue after solidifying was recrystallized from 500 ml. of 96% byweight ethanol to give 210 g. of N-(tributylplumbyl)imidazole (93% yieldbased on the hydroxide, 71% based on lead dichloride).

PREPARATION OF COMPOUNDS 16, 21 AND 22 A mixture of 20 g. (0.05 mole) oftributyllead hydroxide and 4.2 g. (0.05 mole) of cyanoguanidine in 350ml. of ether was stirred at room temperature for threefhours. The white,insoluble solid appeared to reach an irreducible minimum, and solidanhydrous sodium sulfate was added. The mixture was stirred anadditional 0.5 hour, then filtered. The filtrate was stiripped ofvolatiles under vacuum. The residue was 20.3 g. of yellow viscous oil.

, Analysis.-Calcd. for C I-I N Pb: Pb, 44.9%. Found: Pb, 45.7% (by flamephotometer) and 46.4% (by X-ray fluoresence) Infrared analysis confirmedthe proposed structure of compound 16.

Compounds 21 and 22 are prepared in the same manner as compound 16above, except that triethyllead hydroxide and triheptyllead hydroxiderespectively are employed in place of tributyllead hydroxide.

The preparation of the above-mentioned cyanoguanidine compounds isfurther described in a copending application by Worrel, filed on Dec.13, 1966, Ser. No. 601,347, now US. Pat. No. 3,436,414 dated Apr. 1,1969.

In the following table, there are listed the physical properties andanalyses of some of the compounds of the invention.

TABLE II M.P. or de- Analyses percent composltion Compound temp., 0.Found Caled.

HC-N D.I. 10011 N 7. 49 7. 75 H II Pb 57.06 57. 32 HC\ /CH Pb-( 2 5)s(N0. 2, Table I) M.P. 48-60 N 6. 20 6. 29 (No. 12, Table I) M.P. 167 Pb46. 49 46. 50

N Pb-(O1H5)a N Hz("]---lfil' M.P. 178-181 N 15. 52 14. 84

N\ /OH N-Pb-(C2H5)3 (N0. 4, Table I) M.P. 116-118 N 12. 45 12. 14 Pb44.83 44. 89 (No. 3, Table I) M.P. 104-105 C 45. 70 46. 04 H 6. 37 6. 51(N0. 5, Table I) M.P. 103 N 9. 04 8. 46 Pb 42. 07 41. 72 (No. 1, TableI) D.'I. 126-127 N 9. 71 9. 55 Pb 70.82 70.64 (O4Hg)3PbNHCN 011 N 6. 346.68 Pb 49.60 49. 38

The above compounds have been found to be highly valuable as additivesto lubricating oils particularly hydrocarbon oils for the purpose ofpreventing abrasive wear and scuffing or seizure under boundarylubrication conditions. They may also be used with similar effect inhydrocarbon base greases, such as greases thickened with lithium12-hydroxystearate.

I Illustrative examples of hydrocarbon oils to which may be added thenovel compounds herein disclosed are naphthenic base stock, paratfinicbase stock or a mixture thereof. Such oils are often known as the WestCoast crude, the Pennsylvania stock, or the Mid-Continent stock. Thenovel organolead compounds may also be added to synthetic polyester oilswhich are esters of polycarboxylic acids such as sebacic acid, adipicacid, azelaic acid, and the like, synthetic polybutene lubricants whichare formed from the polymerization of isobutene, and other syntheticlubricants such as polyalkylene glycols, tetrahydrofuran polymer oils,phosphate esters, aromatic ethers, and the like.

While the compounds of the invention are valuable lubricating oiladditives per se, their action is enhanced to a considerable degree bythe addition of a phenolic type of antioxidant, e.g. the hereindesignated antioxidant A, to be more fully identified hereinafter. Inparticular, the action of the antioxidant is in many cases to increasethe wear value of the lubricating oil at a higher temperature, e.g., 125C. It also has the beneficial effect of increasing the solubility of thelead nitrogen compounds of the invention, thus enabling compounds thatare otherwise too sparingly soluble in the oil to be used.

The principal tests indicating the value of additives for the purposesabove mentioned were conducted in the Shell 4-Ball Wear Tester, awell-known device, the details of which may be had from the descriptionthereof contained in Lubricating Engineering, vol. 1, p. 35, 1945. Inthis device, a one-half inch metal ball is rotated under a specifiedload against three similar balls clamped together in an equilateraltriangle. These balls are contained in a heated cup filled with thelubricant. The bulk tem- 8 ment, until the average scar diameter hasincreased to 0.47 mm., corresponding to zone pressure of 50,000 psi. Thetime required to reach this scar diameter is designated as the weartime. Effective antiwear additives may increase the wear time from 11-18minutes to 100 minutes or more.

Tests of the above named compounds carried out in the 4-Ball Tester inmineral oil as above described are shown in Table III. The mineral oilused is a commercial product (Humble Oil Co.) designated by Bayol 85, ahighly-refined paraflinic white oil of viscosity 17 centistokes at 100R, which is widely used in lubrication studies. A solution orfinely-divided suspension of the additive was used in an amountsufficient to provide 1% by weight of lead in the oil.

TABLE III.PROPE RTIES OF DIFFERENT ANIIWEAR COMPOUNDS 15 (0.1% Pb)-..Yes. High High 16 Yes Low Low 17 Yes Med High...- 18 Yes--." Low o YesMed Med Yes... High High Yes Low Low Yes.-. Low Low 1 Antioxidant A is4,4-methylenebis(2,6-di-tert-butylphenol). It was used in the concentration of from 0.5 to 1.0 Weight percent of oil. In general, colorreaction with antioxidant A is indicative of favorable action of theantioxidant in conjunction with the additive in the 125 0. test.

2 The solubilities of additives 3, 4, and 5 were not determined but arebelieved to below. Columns 3 and 4 give solubilities with and withoutantioxidant added. In general, low means a solubility of 0.1 percent orless by weight of the oil; med. (medium) means 0.5 weight percent; andhigh means over 1.0 weight percent.

3 In the tests of additives 4 and 8, the oil contained 0.6 weightpercent of antioxidant A.

4 The test was terminated at 900 minutes and had no evidence of wear.

perature of the lubricant is measured by a thermocouple inserted in athermowell in the cup. Torque on the lower ball holder is a measure ofthe frictional resistance at the rubbing surfaces, and is continuouslymeasured by means of a strain gauge and recorder. The rubbing of theupper ball in the presence of the lubricant against the lower threeproduces circular concave scars on the lower balls.

With no wear, the balls will have a minimum scar diameter (Hertzdiameter) which is the result of plastic deformation of the balls, andis determined by the modulus of elasticity of the material and the loadapplied. After a wear run, the three scars are measured to 0.01 mm.under a microscope, and the average diameter of the scars is a measureof the wear, and the basis for computation of the unit pressure.

The pressure in the contact zone of balls in the 4-Ball Test decreasesgreatly during the course of the test, since the load remains constant,while the wear scar area supporting it, increases. For example, with a15 kg. load on AISI 521000 steel balls, the scar diameter isapproximately 0.22 mm., which corresponds to a pressure of 230,000lbs./in. When the scar diameter reaches 0.5 mm., the pressure hasdropped to 45,000 lbs./in.

One type of 4-Ball Test is designed to measure resistance to abrasivewear. In this test, the bulk lubricant temperature is held at C. or at125 C., the rotational speed is 1800 rpm, and the load is 15 kg. Thetest is continued, with periodic interruption for measure- As will beevident, solubility of the additive in the oil is an important factor indetermining its suitability. A number of compounds which have astructure which should enable them to qualify as additives turn out tohave too low solubility. In some instances, the additives show up betterin the wear-time tests than their solubility would warrant. Theexplanation is that in these tests, the additive in suspension iseffective. Therefore, for practical utilization, the solubility factormust be taken into consideration along with the wear-time factor.

The effect of pre-heat-ing the mineral oil-additive solution wasascertained by heating such mixture for two hours at C. in the test cupof the 4-Ball Tester before starting the wear test at that temperature.In the case of compound 4, such preheating raised the wear time at 125C. from minutes to in excess of 1560 minutes.

While antioxidant A improved the action of the addit-ives at 125 C., itdid not, of itself, show any antiwear activity. Thus, when present in anamount of 0.5 Wt. percent of the oil, the wear-time was substantiallythe same as indicated for the clear oil alone in the first line of theabove table.

Tests of additive compound 2 dissolved in mineral oil at varyingconcentrations are described in Table IV. These tests are carried out inthe same manner as described for Table III. The amount of compound 2tested is suflicient to provide a solution of the additive at the givenpercentage of lead.

TABLE IV.ANTIWEAR TESTS OF 0M]? 0 UND 2 Percent Temper- Wear Percentantiature, time, lead oxidant 0. minutes As will be evident, theadditive provides long wear times compared to clear mineral oil. Also,it will be 6V1- dent that while the wear time increases with thepercentage increase in the amount of lead, the additive is effectiveeven in such small concentrations as 0.01% lead.

A second type of 4-Ball Test, using a commercial nonadditive lubricatingoil was designed to measure the protection against sending or seizureafforded by the oil under extreme pressure (E.P.) conditions of boundarylubrication. In this test, a series of separate runs, each one for onehour, was carried out at ditferent loads progressively increasing upto amaximum of 50 kg. The oil temperature was 110 C. or 75 C.; therotational speed was 1800 r.p.m. Upon reaching a critical load theonehour scar diameter increased abruptly from about 0.5 mm. to 1.5-2mm., as a result of scufling and seizure. This critical load testconstitutes an important evaluation of automotive engine oils, for whicha critical load of 45 kg. is sometimes chosen as the minimum acceptable.

Compounds 2, 7, 11 and 15 were selected for submission to this criticalload test, as shown in Table V.

1 At 75 C.

A control test in which antioxidant was present, but no lead waspresent, developed a scar diameter of 1.58 mm. at a 30 kg. load at 110C. in 60 minutes. At 40 kg. load the scar diameter was 1.86 mm. Theestimated critical load was 26 kg.

It will be noted that when the concentration of lead was reduced to thelow level of 0.2%, the critical loads for compounds 2, 11 and 15 werestill in a satisfactory range; i.e., above 44 kg. Doubling the amount ofantioxidant A was of no further benefit to compound 2. At 75 C. therewas comparatively little wear in the presence of compound 2, even at 50kg. load. Compound 7 was somewhat more etfective than compound 2.

In addition to an antiwear agent and an antioxidant, adetergent-dispersant additive inter alia is also recommended for afinished premium motor oil. It was found that the compounds of thisinvention were entirely compatible with known detergent dispersants,asfor example, 2.0% Orom'te 1200, a commercial ashless-type materialwhich is a reaction product of alkenyl succinic anhydride andtetraethylene pentamine wherein the alkenyl radical has a molecularweight about 10004200. Further, the compounds of the invention were alsocompatible with rust inhibitors, commonly used in present day automotiveengine oils, as for example 0.5 Bryton C-45 (a. commercial materialcomprising an overbased calcium sulfonate, molecular weight 400-600).Further, under some conditions of use, a well-known corrosion inhibitormay be used with advantage, as for example, 0.5% Amoco 48 (a commercialmaterial of unspecified composition, believed to be a sulfurizedterpene). The latter type additive is particularly useful where the oilwill come into contact with copper, as for example, in the bearings orshaft. In lubricants containing such additives as specified above, theamount of lead compound required may vary from a maximum of 1% lead,based upon the Weight of the oil, to as little as about 0.01%,preferably at least about 0.1%

The antiwear elfectiveness of the compounds of the invention is in noway diminished by the presence of these other useful oil additives, butmay even be increased thereby. For example, wear tests were made of acommercial SAE 20 oil containing 0.5% lead as compound 2 and 1%antioxidant A, together with the detergentdispersant, rust inhibitor,and corrosion inhibitor cited in the preceding paragraph. In the 4-Bal1Test at 15 kg. load, 50 C., there was no visible Wear after 3000minutes. In the critical load test at C., the scar diameter at 50 kg.load was only 0.82 mm., indicating a critical load value of over 50 kg.

The compounds of the invention, when used as additives to lubricatingoil, were subjected to other known test procedures including:

( 1) RUST PREVENTION TEST This is an adaption of an established test(ASTM D- 665) of the rusting tendency of turbine oils. A roughsurfacedsteel spindle is immersed in the test oil for 24 hours at F. and the oilkept saturated by stirring in water, or (in a modified test) withhydrochloric acid.

(2) PANEL COKER TEST This is a thermal stability bench test developed byEthyl Corporation, of the type widely used in other laboratories. Analuminum alloy panel 1.5 x 3.5 inches in size is heated in a closed boxfor 10 hours at 550 F. Once every minute, hot test oil is sprayed ontothe panel in an established pattern for a period of v5 seconds. Theremaining 55 seconds aiford an opportunity for the oil film to form anadherent deposit of coke. At the end of the test, the appearance of thepanel is observed and the total weight increase is measured.

(3) POLYVERIFORM TEST This is a well-known bench test that measures thetendency of the oil to oxidize and the consequent corrosion ofcopper-lead bearings.

(4) OLDSMOBILE CAM AND TAPPET WEAR TEST In this test a 1960 Oldsmobileengine is fitted with calibrated valve lifter springs having 50% greaterforce than normal and is operated under standard conditions and theamount of scufling to the cams and valves measured.

(5) L-38 OIL OXIDATION TEST factorily to pass these several tests.

Table VI below reports the results obtained from the above-describedtests for an oil containing 0.5 weight percent of lead as compound 2 andfor a high-quality 11 commercial oil. The oil which contained compound 2was a clear SAE 20 oil which also contained one percent antioxidant A, 2percent Oronite 1200 detergent-dispersant, 0.5 percent Bryton C-45 rustinhibitor, and 0.5 percent Amoco 48 corrosion inhibitor. All percentagesare by weight.

TAB LE VI High- Oil quality Test procedure and containing commercialobservations made compound 2 oil (1) Panel coker:

Weight increase, mg 7 50-200 Deposit color (2) Polyveriform:

Bearing weight loss, mg 8 15 Acid number 2. 1 3 Percent viscosityincrease, 100 F 25 80 (3) Oldsmobile cam-and tappet, average wear, inchX 10 Cams 0. 18 0. 2-0. 3 Lifters 0.28 0. 3 .6 (4) L38 engine:

Bearing weight loss, mg 5 19 Appearance of bearing Piston varnish ratingl0 9 Acid number increase 1, 6 1. 8 Percent viscosity increase 1 None.

2 Tan-black. Clean.

4 Dull or Bright.

Even concentrations smaller than reported above in Table VI, such as0.1% lead as compound 2, have proven satisfactory in the Panel CokerTest. Using an SAE 10 oil containing 0.5% antioxidant, clear deposits ofonly 7 mg. were obtained. Similarly, 0.1% lead as compound 11 producedtan deposits weighing 33 mg. in the Panel Coker Test using mineral oiland 0.1% antioxidant.

Lubricating oil containing compound 2 was also added to isooctane forthe lubrication of a two-cycle outboard engine and proved to be apowerful antiwear agent. As little as 0.047% lead in the oil or 18 partsper million in the fuel-oil blend completely prevented wear. Onehalfthis amount produced substantial reduction thereof.

What is claimed is:

1. A composition consisting essentially of a hydrocarbon lubricating oilor grease in lubricating amounts and an additive therefor in Wearingreducing consisting essentially of the compound of the class consistingof (a) trialkylplumbyl cyanamide and trialkylplumbyl cyanoguanidine inwhich the alkyl group has 1 to 12 carbon atoms;

wherein X=N, CH or CR Y=CH, C0, CR, or N when X is CH or CR R=alkyl or 1to 12 carbon atoms R'=phenyl and alkyl of 1 to 20 carbon atoms R=H, NHNHR, alkyl having 1 t0 4 carbon atoms, or phenyl R'=phenyl and alkyl of1 to 20 carbon atoms wherein X and R have the meaning defined aboveunder (b), but the total number of carbon atoms included in the group Rand R is at least 8.

2. The composition of claim 1, in combination with an oil solubleantioxidant.

3. The composition of claim 2, in which the antioxidant is bis(alkyl,hydroxyphenyl)methylene, present in the amount of about 0.1 to 1.0percent by weight.

4. The composition of claim 1, in which the organolead nitrogen compoundis present in the amount of at least about 0.01 percent by weight,calculated as lead.

5. The composition of claim 1 in which the organolead nitrogen compoundis N-(trimethylplumbyl) cyanamide.

6. The composition of claim 1 in which the organolead nitrogen compoundis N-(tributylplumbyl)imidazole.

7. The composition of claim 1 in which the organolead nitrogen compoundis N-(tributylplumbyl)benzimidazole.

8. The compound of claim 1 in which the organolead nitrogen compound is3 amino N (tributylplumbyl)- 1,2,4-triazole.

9. The composition of claim 1 in which the organolead nitrogen compoundis 3 anilino 5 isopropyl N (tributylplumbyl) -1,2,4-triazole.

10. The composition of claim 1 in which the organolead nitrogen compoundis 3-amino-5-phenyl-N-(tributylplumbyl)-l,2,4-triazole.

11. The composition of claim 1 in which the organolead nitrogen compoundis N- (tributylplumbyl)benzotriazole.

12. The composition of claim 1 in which the organolead nitrogen compoundis N-(triethylplumbyl)4,5-diphenylimidazole.

13. The composition of claim 1 in which the organolead nitrogen compoundis N-(tributylplumbyl)-2-undecylbenzimidazole.

14. The composition of claim 1 in which the organolead nitrogen compoundis N-(triethylplumbyl)-2-methyl imidazole.

15. The composition of claim 1 in which the organolead nitrogen compoundis N-(triethylplumbyl)-4-methyl- 5-( l-ethyl-pentyl imidazole.

16. The composition of claim 1 in which the organolead nitrogen compoundis N (triethylplumbyl) 2 undecyl imidazole.

17. The composition of claim 16 in which the undecyl group of theorganolead nitrogen compound is branched chain.

18. The composition of claim 1 in which the organolead nitrogen compoundis N-(triisobutylplumbyl)imidazole.

19. The composition of claim 1 in which the organolead nitrogen compoundis N-(triethylplumbyl)imidazole.

20. The composition of claim 1 in which the organolead nitrogen compoundis an N-(trialkylplurnbyDcyanoguanidine, said alkyl group having 1 toabout 12 carbon atoms.

21. The composition of claim 20 in which the alkyl group is ethyl.

22. The composition of claim 20 in which the alkyl group is butyl.

23. The composition of claim 20 in which the alkyl group is heptyl.

24. The composition of claim 1 in which the organolead nitrogen compoundis N-(trialkylplumbyl)imidazole in which the alkyl group has 1 to 12carbon atoms.

25. The composition of claim 1 in which the organolead nitrogen compoundis N-(trialkylplumbyl)imidazole in which R is alkyl having 1 to 12carbon atoms and R is alkyl having 1 to 20 carbon atoms.

26. The composition of claim 1 in which the organolead nitrogen compoundis N (trihepty1plumby1)imidazo e.

27. The composition of claim 2, plus a corrosion inhibitor.

28. The composition of claim 2 which includes a detergent-dispersant.

29. The composition of claim 1, in which the organolead nitrogencompound is present in the amount of at least about 0.1 percent byWeight, calculated as lead.

30. The composition of claim 1 in which the organolead nitrogen compoundis N-(triethylplumbyl)-2-ethy1- 4-methyl imidazole.

31. The composition of claim 1 in which Y is CH, CC, or N when X is CHor CR.

32. A composition consisting essentially of a lubricating oil or greasein lubricating amounts and an additive therefor in wearing reducingamounts consisting essentially of the compound of the class consistingof (a) trialkylplumbyl cyanamide and trialkylplumbylcyanoguanidine inwhich the alkkyl group has 1 to 12 carbon atoms;

X=N, CH or CR Y=CH, Cfi, CR, or N when X is CH or CR R=alky1 or 1 to 12carbon atoms R'=phenyl and alkyl of 1 to 20 carbon atoms BC I Hg :5 It

Pb-Rs wherein X and R have the meaning defined above under (b), but thetotal number of carbon atoms included in the group R and R is at least8.

References Cited UNITED STATES PATENTS 2,783,243 2/ 1957 Rudner 25251 X2,805,996 9/1957 Deger 25233.6 3,287,265 11/ 1966 Perilstein 25242.73,303,132 2/1967 Leonardi 25249.7

DANIEL E. WYMAN, Primary Examiner W. H. CANNON, Assistant Examiner US.Cl. X.R.

" UNITED STATES PATENT OFFICE CERTIFICATE OF CORRECTION Patent No.3,527,70 Dated September 8, 1970 Inventor) Warren L. Perilstein andHarold A. Beatty It is certified that error appears in theabove-identified patent and that said Letters Patent are herebycorrected as shown below:

Column 5, 7 line 69, change "stiripped" to stripped Column 7, line 67,change "AISI 521000" to AISI 52100 Column 8 line 9, change "designatedby Bayol" to designated Bayol Column 8, Table III, (column 7) change"antioxidant" to antioxidant A Column 8, Table III, Item 12, column 6,change "150 K" to 150 Column 11, Claim 1, line 3, change "wearingreducing" to wearing reducing amounts Column 12, Claim 8, line 1, change"compound" to composition Column 13, Claim 32, line 6 change "alkkyl" toalkyl Signed and sealed this l th day of May 1971.

(SEAL) Attest:

EDWARD M.FLETCHER, JR. WILLIAM E. SCHUYLER, JR. Attesting OfficerCommissioner of Patents

